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Use of Chemicals to influence Maillard reaction and flavor

April 9, 2013 - 4:17pm

michaelreeves

Use of Chemicals to influence Maillard reaction and flavor

Hi All,

I have questions concerning the use of chemicals for dipping baked goods into. Specifically pertaining to pretzels. Specifically these chemicals- Lye, Potassium Hydroxide, Calcium Hydroxide (Lime), Sodium Carbonate, Baking Soda, Salt, and Alkaline Water. My reasoning for choosing all of these ingredients is because they are alkaline and influence the Maillard Reaction. Which is essentially where the color and taste of a pretzel comes from.

1) Does anyone know what are the common or rare/secret ingredients, used in the browning solution that gives pretzels their color and taste? I know Lye (NaOH, Sodium Hydroxide, Caustic Soda) is the main ingredient responsible for the distinct flavor/color, as well as baking soda and sodium carbonate (Washing Soda) being the more common ones used.

2) I've never used Potassium Hydroxide (Caustic Potash, KOH), but I know it has similar properties as Lye. Does anyone know its affects on flavor? I know it influences the Maillard Reaction.

2a)Also, I plan to mix these chemicals together in water, are there any adverse effects when mixing these two togther?

3) Does anyone know if alkaline water would be better suited for my needs instead of tap or filtered water? I figure it couldn't hurt considering the objective is to increase alkalinty in the solution to enhance flavor and color. The soltuion is already becoming alkaline with the addition of any of the chemicals listed.

4) I've seen some browning solutions contain salt in addition to lye, but never any of the other ingredients previously listed. I have very limited knowledge and experience with Chemistry, so I don't want to just go a head mixing up strong alkalie solutions and injure myself. Does anyone, with reputable knowledge of Chemistry, have any ideas if I can mix Lye, Sodium Carbonate, Calcium Hydroxide, Potassium Hydroxide, and Salt, in multiple combinations of ingredients and amounts?

4a)Also, when mixing the lye bath, the goal is a 4% or weaker solution. If I add other alkaline ingredients, how will I have to compensate to still achieve a 4% solution?

4b)Or should the solution total 4% of whatever ingredients being added to the solution? Meaning, in 1000g of water I only have 40g to play with. Do all the ingredients added have to total 40g?

4c)Or can I just add 4% of each ingedient, meaning, each ingredient is 40g in 1000g of water. For example, if I have 1000g Water and I add Potassium Hydroxide and Lye, should I add 40g of each ingredient equalling 4% each, but now totaling 8%?

Example 4b)

1000g Water

20g Lye= 2%

10g Potassium Hydroxide= 1%

5g Sodium Carbonate= .5%

5g Salt=.5%

Total= 4% Alkaline Solution

OR

Example 4c)

1000g Water

40g Potassium Hydroxide= 4%

40g Lye= 4%

80g combined= 8% Alkaline Solution

How alkaline of a solution can only be determined with a pH meter/strip.

I realize that these ingredients all do the same thing, just in varying degrees, which is why I'm interested to know their effects when mixed together. It's not about picking which is best, but which are best together.

If you don't know about all of the ingredients, the most important ones to consider are the Lye, Potassium Hydroxide, Calcium Hydroxide, Sodium Carbonate (in order of importance), and how they react together, and any insight into their effects on flavor.

I cannot provide a specific answer, but would suggest you look more into the commercial side of browing agents for details. Here's an example with some referenced patents that will give you some ideas:

There's a company called red arrow that specializes in browning agents that may already have a product available. I can pretty much guarantee that anyone with the specific answers is in the food chemestry industry and would consider an answer proprietary information, but the link may give you some help.

2. Be extremely careful with dry lye, it can cause severe chemical burns. When mixed with water it releases a lot of heat, so much that the solution might boil, so dissolve it in small portions in plenty of water in large jar.

3. You can't count alkalinity the way you do, one gram of lye is not equal to one gram of soda or KOH.

I realize that they all have different densities and intensities. How would I properly calculate the concentration of my solution? All of the recipes for a caustic bath only describe it in units of percentages, and mention nothing of the concentration, other than not going over 4%. I think I'll need a device/technique for determining the strength of each individual ingredient that's in the bath, as well as a certain limit to the alkalinity of the solution, pH tester?

You said it yourself: without some chemistry knowledge & experience it is not smart to play around with strong alkali (basic) materials; the compounds that you mention are all capable of causing moderate to severe chemical burns; a splash in the eye could be disastrous. They should always be handled wearing rubber gloves.

While the chemicals that you have mentioned are all compatible with one another, except for baking soda which can vigorously react with the others, blindly mixing them is not advised nor likely necessary to produce the desired results.

Suave's warning about mixing alkaline chemicals, especially very strong ones, cannot be overemphasized: always add the chemical in small amounts to a stirred volume of water that is large enough to safely dissipate the heat that is produced by the reaction of the alkalai and water--and in a non-reactive container (e.g. avoid aluminum).

How about backing up a step and describing what have you used to date, what results have you got and what is your problem/shortcomings?

I currently use lye and I've used baking soda. I know how to properly prepare a caustic bath and all the dangers that accompany it. My knowledge ends when it comes to using more than one chemical, which is my reasoning for the questions, because I know better than to mix things up.

My results with baking soda were a toned down taste of what a german pretzel should be. The color is a medium brown/golden brown. For me it was obvious this was not what I wanted.

My results with lye have been satisfactory in color, but seems to still be lacking a flavor as strong as the ones I've had in Germany and Local bakeries in L.A. The color is a dark brown with hints or a burnt red, mixed in with golden brown color in the creases.

I really wish I could describe my shortcoming's better. The crumb seems to taste a little like white country bread and not close to the pretzel I'm using to compare mine against. The pretzel I try to emulate has a medium sized crumb, and seems to carry that exterior flavor from the caustic bath into the dough. It also has a noticeable tang the second it hits your tongue, with a certain creamy and chewy texture. I believe they are sourdough pretzels. I've used different preferments such as a poolish and biga. The next batch I cook will be sourdough, so I'm hoping that will put an end to my quest. I plan on doing the sourdough first, before I go ahead and start using chemicals.

I will re-post this here for the chemists to comment on why baking normal dry baking soda makes it stronger.

Yesterday, I took regular baking soda and baked it for half an hour 200°C, wow, did that increase the strength! Plan on dissolving as much as I can in a shallow glass or plastic non-reactive pan of cooled (boiled) water and using this water to soak shaped rolls for about 10 to 20 minutes of the proof rise. Remove and place onto baking parchment or well greased pans, score before bake. They brown like crazy and take on pretzel taste. (I've made thin wormy pretzels but my husband ate them faster than I could bake them!) A great bake to watch and don't let the darkening scare the crap out of you! Use a stiffer dough so it doesn't fall apart in the soak. Heat up the soda soaker when done (vacuum pack in glass jar) or simply save and refrigerate for the next time. Add more of the baked soda and water as needed. (Do not use the baked soda as "baking soda" after this, it is too strong.) Stir up before using again at room temp or slightly warmer if speeding up the rise. Can use your fingers and a slotted plastic spoon. Rub hands in a very thin vinegar solution after playing (under 5%) and rinse.

Alkaline tap water is usually also hard water, and usually contains calcium salts. Calcium salts which are chemically stable tend to be insoluble in water, and probably won't add much to a dip for pretzels.

As others have said above:

1. You can't measure the chemical effect of materials using identical weights. You have to take into account the atomic weights of the elements in the compounds. To put it in human terms, a small person and a large person may be able to perform the same function, but the large person will weigh more. Hiring people by total weight would not accomplish the goal of having a particular size task accomplished. For that, you need to count the people, not their weights.

2. You are likely to get heat given off when you dissolve some of them. This causes the water to boil, and the aerosol given off can cause lung damage if you breathe it in by accident.

3. Potassium salts taste strange. Try a salt substitute based on KCL and see for yourself.

I would suggest trying a sodium carbonate (washing soda) treatment if the sodium bicarbonate (baking soda) treatment doesn't fit your needs. If you must try the sodium hydroxide (lye) treatment, be extremely careful.

Some people add sugar to the dip, to get more brown color.

MiniOven: Baking sodium bicarbonate causes it to decompose into sodium carbonate with a loss of water and carbon dioxide. I am a chemist by profession, which is why you would never get a grade for any type of bread in a class that I was teaching. *wink*

but it works much better than the straight baking soda. The sodium carbonate weighs slightly less dried out but it dissolves better in the water. Why? don't know why, but the crust tastes better and works better. I let it cool before packing into a jar.

Tasting the baked baking soda on the other hand tastes awful, I wet my finger and then pressed it into the powder and onto my tongue. Yuck, double yuck. Spit and rinse yuck! :(

Sodium carbonate is a stronger alkali than sodium bicarbonate because it can react with two hydrogen ions (as in the acid HCl) rather then just one, before it is no longer alkaline.

washing soda:
Na2CO3 + 2 HCl => 2 NaCl + CO2 + H2O

baking soda:
NaHCO3 + HCl => NaCl + CO2 + H2O

Washing soda actually turns partially back into baking soda along the way to becoming table salt, in the above example.

Sodium carbonate is washing soda. I haven't tasted any of that but I don't expect that it tastes good. We weren't evolved to eating cleaning materials. *smile*

The washing soda you get from the baking soda that you baked weighs less than the baking soda because water and carbon dioxide have left it. Baking soda has a molecular weight of 84. Washing soda has a molecular weight of 106. It takes two molecules of baking soda to make one molecule of washing soda. That means that 168 grams of baking soda will bake down to 106 grams of washing soda. 44 grams of carbon dioxide will have left, as will have 18 grams of water. Notice that 106 + 44 + 18 = 168.

Here's a link to Harold McGee's article on making baked baking soda (turning baking soda into sodium carbonate) for making pretzels. It's full of great food chemistry info, as are most of his missives :)

The various posts regarding the use of lye and other industrial chemicals in home baking causes me to offer this cautionary tale. I am also a woodworker and I like to build "Mission" style furniture. As you may know, in the old days they achieved that deep brown color on Mission oak furniture by creating an airtight fuming chamber and exposing the quarter-sawn oak boards to very strong ammonia fumes for hours or days until the wood turns a beautiful dark rick color. I cleverly located a source of industrial ammonia and built my home wood fuming chamber out of heavy gauge plastic in my garage. I will skip over the details and just say that I nearly killed myself and another family member in the process. I decided that using wood stain to achieve color - while not as authentic as ammonia fumes - is a hell of a lot safer and I am now willing to sacrifice authenticity for safety.

If you are going to use and store lye or other industrial chemicals in your home for baking, please be extremely careful, especially if you have curious kids. Personally, I would rather skip the chemicals and enjoy tasty and safe if not entirely authentic bagels.

There is a subtantial difference in scale between making a small dilute waterbath (tsp or two lye per qt up to 1-2% by weight) and filling one's garage with ammonia fumes. Ammonia is gas which can be used as a saturated water solution--but one that will release gas as you must have found out. Lye is a solid which dissolves in water--and stays there. As many know, lye is the active ingredient in Drano and most of the consumer drain treatments; sodium carbonate has been sold for years at retail as a pool chemical or laundry aid. The take home message is: Lye and Sodium Carbonate can be safely used at home in a bagel or pretzel bath as long as one understands and respects their chemical properties.

Everyone: don't forget, when disposing of your lye bath, you can wash it down the drain with a large excess of cold water (slowly pour the aqueous lye solution into running water, avoid splashing). A lye solution can be also be neutralized by slowly pouring vinegar into the solution while gently stirring until the mixture stops fizzing. The key is moderation, mix small amounts in at a time, don't dump chemicals together. Neutralizing is better if you have a septic system. It is always prudent to wear eye protection when working with liquid chemicals--even dilute solutions or relatively innocuous things like many items found in the home.

Pretzel style. I rolled a half way proofed roll around in my fresh mixed baked-baking-soda and water solution for about 5 minutes and then let set them on parchment continue proofing. I baked 4 examples with steam (the rest of the dough is retarding) and scissors scored them. They are very tasty and pretzel like and almost too dark but baked just right. The insides are tender. The outside crust is soft after cooling and stays dull. Pretzel recipes contain water and no milk, so i think milk giving me the soft crust. It would be better with a shine and some salt. I think I will also dunk for a shorter period of time and make some long twists.

Never mind the little surface bumps, I threw in some crushed cooked chestnuts (first of the season!) into the dough and they didn't fall apart like the potato. I am more than happy with the taste and the color.

Hope you'll post back on more baked baking soda results, yours are coming out much better than mine (I tried it when Harold McGee's article first came out), which didn't get very dark. I boiled mine in sodium carbonate solution, perhaps it wasn't a strong enough solution. I do remember them being shiny, though :)

We are only considering very mildly alkaline solutions (Yes, the hazard is actually minimal, but for people with limited to no experience, one should always err on the side of safety. That will provide a greater safety margin if someone makes a mistake and produces a more concentrated solution than intended).

There are two things we want on the surface of bagels and pretzels: gelatinization and caramelization. Both of these occur under similar conditions. Water is required for starch gelatinization, some alkali speeds it up; proteins are hydrolyzed to amino acids for Maillard reactions (responsible for caramelization/browning), alkali catalyze this; and, starches can be converted to sugars. Heat accelerates all these processes. Time makes a difference, too, and alkali concentration is also a factor to a point for gelatinization.

Pretzels are typically darker than bagels and that is why bagels, if boiled at all, use plain water vs a lye solution for pretzels.

A casual search of published research and patents shows that lye is the best choice for browning and gelatinization. Sodium carbonate apparently does not accelerate gelatinization, but does affect browning; if this is correct, those using it should see good color, but not as much skin thickening. I'd guess that sodium carbonate will accelerate gelatinization, it just takes a much stronger solution and or more time.

Both caramelization and gelatinization require heat, so raising the temperature of the bath will increase rates. 100-125F at home should be a good compromise between efficacy and safety.

Wheat starch will gelatinize in water, adding a strong alkali (base) speeds it up greatly. Apparently, there is a sweetspot for alkali concentration; for gelatinization of wheat starch with lye it's in the realm of 3-5% (lye by weight) which is very manageable and safe in a home environement. More does not necessarily get you more gelatinization, maybe greater & quicker color, though.

Time favors both caramelization and gelatinization. However, since we are just looking for surface modification of our bagels, they only need be treated long enough for the surface to absorb some of the solution. This implies seconds of exposure, not minutes.

As has been noted above, sodium carbonate is not a direct replacement for sodium hydroxide (lye), it will take about 26x (by weight) as much sodium carbonate to match the strength of a given sodium hydroxide solution (Mango: is my math right re mol wt and pKb differences? It's been a while...). This is not practical and one of the reasons why lye is prefered over soda ash for this use. Sodium carbonate can be used for dipping bagels and pretzels, but at 2-5% by weight it will take longer than a comparable lye solution at equivalent temperatures to produce a similar effect. Baking wise, I'd rather do things to minimize the dipping time.

Anything which increases the sugar on the surface will enhance the color such as adding some diastatic malt or even adding sugar to the dipping solution, I suppose.

Mini: 5 min dip (exposure) seems like a long time to me. Absorbing too much liquid may result in an excess alkali residual and unfavorble taste. Your #1 option could remove alkali from the surface which is also undesirable; you want some of it to remain so that it can react in the oven. In fact, it appears that a cold dip and baking is typical in the commercial world where they are not seeking as tough a crust and want good color (and don't have to pay to maintain a hot dipping bath). Option 3 is redundant. Working with relatively weak aqueous solutions should not require multiple steps.

A lot of applied chemistry is a matter of trade-offs. For pretzels or bagels, I would select an alkali, concentration and time that minimizes the undesirables and allows me to do one dip. That seems to be 3-5% aqueous lye (preferably at 125F or higher) for 30-60 sec in a 400F (give or take) oven.

Disclaimer, of course: I am no longer a professional chemist, i.e. I don't get paid for it anymore and we all know what free advice is worth... ;-)

Peter

p.s. Teflon (flourocarbon) or silicone based non-stick coatings are inert towards the mildly alkaline solutions of sodium carbonate or sodium hydroxide at the temperatures we are using. You can use your pots, glass or polypropylene container. If the teflon was scratched or compromised and some aluminum was exposed, it would not be enough to be dangerous. You might see a little fizzing--not unlike what you see in a glass of soda where bubbles nucleate (form) at a point source. If so, just stop and transfer the liquid to a better container.

Even if neither you nor I are paid to do chemistry these days, if we did it well enough to earn a living by it in the past then I maintain we are still professionals. Maybe instrumentation has gotten more complicated, but carbon is still tetrahedral and Avogadro's number hasn't changed.

4% sodium hydroxide by weight would be 40 grams of sodium hydroxide in 1 liter, or a 1 M solution. Sodium hydroxide is a strong base. Sodium carbonate is a weak base. There is no concentration of sodium carbonate that would equal the alkalinity of a 1 M solution of sodium hydroxide. Even a 0.1 M solution of sodium hydroxide is more alkaline than any aqueous solution of sodium carbonate. The best answer to the question of how much sodium carbonate would be required to re-create the alkalinity of most sodium hydroxide dipping solutions is probably "You can't get there from here."

However, you might get a pretzel you like with sodium carbonate solution. *smile*

Mango: as we are talking about 1M lye solutions, you're right, of course--I should have remembered that. (If we are talking about something less than 0.01 N, I might have had a leg to stand on; not that it would make any difference here. lol)

Yep, 0.01 N would be a different game. It occurs to me this morning that we should have been able to do a reality check at the point where someone suggested multiplying 4% times 26. *weak giggle* Isn't retirement fun?

I baked 120g of baking soda in a 200°C oven for 30 minutes. Let it cool and placed the roughly 75g of sodium carbonate carefully into a jar trying not to make too much dust. When ready to use, I poured 600g cold tap water into a plastic bowl and slowly added the sodium carbonate while stirring gently to dissolve. As I had made it the day before it had cooled to room temp but when fresh, it is as warm as bath water approx. 36°C.

I boiled a small saucepan of water. I found a stainless steel bowl so I was now prepared to warm up the sodium carbonate solution to make a few more tests. Water and later sodium carbonate solution heated to 175°F or 80°C

Then I took out my dough from the refrigerator, in this case it was a little over retarded but heck, I knew it would work. I split up the dough into pieces and rolled out some ropes and let them rest before shaping. I made "0, 1, 2, 3, 4" roughly out of dough to mark my experiments. The rest into knots. I will call the Sodium carbonate solution simply a soda bath for ease in reading.

This, 0 to 4 are the top row (left to right) in the picture. All rolls were lightly scored before going into the oven. The second row includes one roll dipped in warm water (5) and nothing else to see the natural color of the dough. The rest of the rolls were knots (of pregnant snake shapes) dipped for 30 seconds in hot soda bath gradually turning my soda bath yellow as well as the skins on the rolls. Baked for 16 minutes at 180°C. Non of them are really shiny but the darker striped ones (hot soda bath) and #1 and #4 (hot water dip followed by cold soda bath) are the darkest with the better crust flavour.

Now to work on beauty... I don't expect anyone to recognize the numbers! I do like those five on the bottom. They have an abalone spiral shape and a dull shine. A soft dough is a bit tricky. Got to mix up some more dough.

Mini- Thanks for your experiment. I got something close to the color I want for pretzel rolls with boiling in baking soda solution followed by egg yolk + milk wash, but that was before I stumbled on this business of baking the baking soda. I think McGee recommends rinsing off the dipping solution, but that seems odd to me when that's not done for the more caustic lye dip. It looks like you dipped, drained, and baked, with no rinse step, right?

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